Trifluoromethyl-sulphonic acid-trifluoromethylphenyl amides and process for their production



3,322,823 Patented May 30, 1967 TRIFLUQRUMETHYL-SULPHONIC ACID-TRI- FLUORUMETHYLPHENYL AMIDES AND PROCESS F01 THEIR PRODUCTION Friedrich Mirth, Leverlrusen-Bayerwerk, Giinter Unterstcnhiiler, Opladen, and Heinz Herlinger, Cologne-Elittard, Germany, assignors to Farbent'abriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Nov. 22, I963, Ser. No. 325,765

(,laims priority, application ermany, Dec. 17, 1962,

F 38,576 4 Claims. (Cl. 260--556) The present invention is concerned with novel trifluoromethylphenyhsulphonic acid-trifluoromethylphenyl amides which show acaricidal properties, and with a process for their production.

It has already become known that trifluoromethylphenyl-sulphonic acid-trifiuoromethylphenyl amides which contain further substituents, preferably halogen, possess insecticidal properties (of. Belgian Patent Specification No. 581,914).

It has been found that trifluoromethylphenyl-sulphonic acid-trifiuoromethylphenyl amides of the formula wherein it stands for a whole number from 1-3, show strong acaricidal properties.

In Formula I, n means preferably 1 or 2. Especially effective are those compounds which contain at least a total of three trifiuoromethyl groups. 1

It has also been found that trifluoromethylphenyl-sulphonic acid-trifluoromethylphenyl amides of the Formula I are obtained by reacting trifluoromethylphenyl-sulphonic acid halides of the formula SC Hal wherein It stands for 1, 2 or 3 and Hal for halogen, especially chlorine, possibly in the presence of bases, with trifluoromethyl anilides of the general formula (III) wherein it stands for l, 2 or 3. The reaction is expediently carried out in the presence of a diluent.

It is definitely surprising that the compounds according to the invention which contain exclusively trifluoromethyl groups, but no halogen atoms, as substituents have a subtsantially higher effectiveness than the compounds known from the state of the art which contain trifluoromethyl groups as well as halogen atoms. Furthermore, it must be called definitely surprising that the compounds according to the present invention, in contradistinction to the most closely related known compounds, are considera bly less phytotoxic in spite of their increased acaricidal effectiveness. This fact renders them especially valuable for combating spider mites. The new products according to the invention represent a substantial enrichment of the art.

If the reaction according to the invention is started from 3,5-bis-trifluoromethylbenzene sulphochloride and 3,5-bis-trifluoromethyl aniline, the course of the reaction can be illustrated by the following scheme of formulae:

trifluoromethyl groups may stand in ortho-, metaor paraposition.

Individual examples are: 3-trifluoromethyl aniline, 4- trifiuoromethyl aniline, 3,5-bis-trifluoromethyl aniline and 2,4,o-tris-trifluoromethyl aniline.

Suitable diluents for the process according to the invention are all inert organic solvents as well as water. In particular, the following may be mentioned: pyridine, dichlorobenzene, dioxan, acetonitrile and dimethyl formamide.

The reaction according to the invention can be carried out with the use of acid-binding agents. This is, however, not absolutely necessary. Suitable acid-binding agents are those usually employed, for example pyridine, triethylamine and potassium carbonate."

The reaction according to the invention can be carried out in a wide range of temperatures. In general, the operation takes place between 0 and 180 (3., preferably between 0 and C.

In carrying out the process according to the invention, the reaction components are applied in equimolecular quantities. It may, however, also be expedient to use an excess of trifiuoromethyl aniline. An especially advantageous method consists in starting with the amine component, optionally together with a diluent, and adding the sulphohalide in portions.

Working up of the reaction mixture is carried out in the customary manner.

The compounds according to the invention exhibit strong acaricidal and ovicidal properties. They can be employed against normally sensitive, as well as resistant spider mites at any stage of development. It must be especially emphasized that the substances according to the invention exhibit only a low phytotoxicity.

The substances according to the invention can be used as such or formulated in the customary manner. Preferred formulations are aqueous emulsions and dispersions, but also dusts may be used. The formulations are prepared with the use of conventional emulsifiers, dispersing agents and extenders.

In the following table, the acaricidal action of two of the compounds according to the invention is shown and compared with the most closely related known derivative.

The tests were carried out in customary manner. The emulsions were prepared by dissolving one part of the agent in four parts of dimethyl-formamide and diluting the concentrated solution to the desired concentrations with water and the use of emulsifier.

TABLE Tetmnychus telarius Normally sensitive Resistant Concentration Destroyed Concentration Destroyed in percent in percent in percent in percent (agent/water) (agent/water) 0. 100 0. 05 100 SONH 0.02 90 0.02 80 0.01 50 0.01

F3 CF:

IigC CF! SONH 0. 05 90 0. 05 100 0.02 80 0. 02 70 F30 CF: BIaC CFa somrro. 05 100 0.02 0 Cl 01 (previously known) The superiority of the products according to the inven- 30 Exarnplg 3 tion is shown by the table. Whereas the compounds ac- 0 cording to the invention do not damage the plants, for I example bean plants, considerable damage occurred by the known compounds. I

The following examples are given for the purpose of F 0 CF;

illustrating the present invention.

Example 1 i NT; (1113;

245 g. of 3-trifluoromethy1benzene sulphoehloride are added portionwise at 05 C. in the course of 1-2 hours to a solution of 228 g. of 3,5-bis-trifiu0romethyl aniline in 1 litre of pyridine, and the mixture is stirred, after warming to room temperature, for 8 hours. It is finally heated at 60 C. for 1 hour and the reaction mixture poured, after cooling, on 2 kg. of ice in 2 litres of 20% hydrochloric acid. An oil thereby precipitates which solidifies, after residual traces of unreacted 3,5-bis-trifluoromethyl aniline have been distilled off with steam. The 3-trifiuoromethy1- benzene 3,5' bis trifluoromethylbenzene sulphonamide can be purified by taking up in aqueous sodium hydroxide and precipitation with aqueous hydrochloric acid. A product of melting point 112 C. is obtained from recrystallisation from alcohol or ligroin.

Example 2 Far ira In an analogous manner, the 3,5-bis-trifiuoromethylbenzene-3'-trifiuoromethylbenzene sulphonamide is prepared from 3,5-bis-trifiuoromethylbenzene sulphochloride and 3-trifiuoromethyl aniline. Melting point: 108 C. (recrystallised from ligroin).

In an analogous manner, the 3,5-bis-trifluor0methylbenzene-3',5-bis-trifiuoromethylbenzene sulphonamide is obtained from 3,5-bis-trifiuoromethylbenzene sulphochloride and 3,5-bis-trifiuoromethyl aniline. Melting point: 113-114 C. (recrystallisation from alcohol).

We claim:

1. A compound of the formula wherein n is a whole number of 1-3, the sum of the trifluoromethyl substituents being at least a total of 3.

2. The compound of claim 1 wherein n is 2.

3. A compound of the formula SO2NII l C F3 C F3 4. A compound of the formula Fat: (11

SO2-NH References Cited UNITED STATES PATENTS 2,618,538 11/1952 Gilbert 167-60 3,034,955 5/1962 Frick et al. 260556 X 3,162,684 12/1964 Frick et al. 260--556 FOREIGN PATENTS 216,493 7/1961 Austria. 900,111 7/1962 Great Britain.

JOHN D. RANDOLPH, Primary Examiner. 

1. A COMPOUND OF THE FORMULA 